TWI704169B - Curable resin composition, dry film, cured product and printed circuit board - Google Patents

Abstract

The present invention provides a curable resin composition, dry film, cured product, and printed wiring board that are excellent in resolution, toughness, and heat resistance.

The resin composition includes: (A) an amide resin having at least one structure represented by the following formulas (1) and (2) and an alkali-soluble functional group,

(B) Inorganic particles with an average particle diameter of 200 nm or less, (C) a photopolymerization initiator, and (D) a compound having an unsaturated double bond. (B) The inorganic particles having an average particle diameter of 200 nm or less are preferably silica, and preferably contain (E) a thermosetting resin.

Description

Curable resin composition, dry film, cured product and printed circuit board

The present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board. In detail, it relates to a curable resin composition that can obtain a cured product with better resolution, toughness, and heat resistance than before , Dry film, hardened material and printed wiring board.

At present, some of the solder resist compositions of printed wiring boards for civilian use and most industrial printed wiring boards are based on the viewpoint of high precision and high density. After being irradiated with ultraviolet rays, the image is formed by development. A liquid development type solder resist composition in which at least one of heat and light is irradiated and hardened (mainly hardened). Among them, based on the consideration of environmental issues, an alkali-developing photo solder resist composition using an aqueous alkali solution as a developing solution has become the mainstream, and has been widely used in the manufacture of actual printed wiring boards.

In the past, alkali-soluble resins, especially epoxy acrylate modified resins, were generally used in alkali-developing photo solder resist compositions. For example, Patent Document 1 proposes a solder resist made of photosensitive resin, photopolymerization initiator, diluent, and epoxy compound by adding acid anhydride to the reaction product of novolak epoxy compound and unsaturated monobasic acid Composition.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 61-243869

At present, as a curable resin composition, phenol novolak type (cresol novolak type) epoxy acrylate resin or acrylic copolymer type resin has been widely used among alkali-soluble types. However, phenol novolac type epoxy acrylic resins are not necessarily excellent in toughness and toughness, and acrylic copolymerized resins have poor heat resistance. Therefore, it is difficult for the conventional curable resin composition to have both high toughness and heat resistance. On the other hand, in recent years, when semiconductor package components are mounted on printed wiring boards, the number of connected IOs has been increased simultaneously with the miniaturization of components, resulting in a rapid increase in wiring density. In order to make high-density wiring possible, a curable resin composition with high resolution is required.

Therefore, the object of the present invention is to provide a curable resin composition, a dry film, a cured product, and a printed wiring board that can obtain a cured product with better resolution, toughness, and heat resistance than before.

The inventors of the present invention actively reviewed the above-mentioned problems and found that by setting the resin used in the curable resin composition to a resin with a specific structure, and setting the particle size of the inorganic particles of the filler to a specific Below the value, the above-mentioned problems can be solved, and the present invention is finally completed.

That is, the curable resin composition of the present invention is characterized by including (A), (B), (C), and (D): (A) has at least the following formulas (1) and (2) One side structure and alkali-soluble functional group amide resin,

(B) Inorganic particles with an average particle diameter of 200 nm or less, (C) a photopolymerization initiator, and (D) a compound having an unsaturated double bond.

The curable resin composition of the present invention may also include a resin having an alkali-soluble functional group having a structure different from that of the aforementioned (A) amide resin. In addition, the aforementioned (B) inorganic particles having an average particle diameter of 200 nm or less are preferably silica. Moreover, it is preferable to contain (E) thermosetting resin. Furthermore, the aforementioned (E) thermosetting resin is preferably an epoxy resin having an alicyclic skeleton.

The dry film of the present invention is characterized by having a resin layer obtained by coating the curable resin composition of the present invention on the film and then drying it.

The cured product of the present invention is characterized by curing the curable resin composition of the present invention or curing the resin layer of the dry film of the present invention.

The printed wiring board of the present invention is characterized by having the cured product of the present invention.

According to the present invention, it is possible to provide a curable resin composition, a dry film, a cured product, and a printed circuit board that can obtain a cured product excellent in resolution, toughness, and heat resistance.

Hereinafter, the embodiments of the present invention will be described in detail.

[Curable resin composition]

The curable resin composition of the present invention (hereinafter also referred to as "resin composition") includes (A), (B), (C), and (D): (A) has the following formulas (1), (2) ) At least one of the structure and alkali-soluble functional group of the amide resin (hereinafter, also referred to as "(A) component"),

(B) Inorganic particles with an average particle diameter of 200 nm or less (hereinafter, also referred to as "(B) component"), (C) photopolymerization initiator (hereinafter, also referred to as "(C) component"), and ( D) A compound having an unsaturated double bond (hereinafter also referred to as "(D) component"). Using the resin having the above structure as the resin component of the resin composition, and using inorganic particles with an average particle size of 200 nm or less as the filler, a cured product with excellent resolution, toughness, and heat resistance can be obtained.

Moreover, the resin composition of the present invention can be developed by a weakly alkaline aqueous solution such as sodium carbonate aqueous solution, potassium carbonate aqueous solution, ammonia aqueous solution, etc., and it is not necessary to use a strongly alkaline developing solution for development. In addition, since it can be developed with a weakly alkaline aqueous solution, the environmental load is less. The resin composition of the present invention has a solubility of, for example, a sodium carbonate aqueous solution (30°C, 1% by mass) of 0.05 g/L or more in 1 minute.

Hereinafter, each component of the resin composition of the present invention will be described in detail.

〈(A) Ingredient〉

The component (A) of the resin composition of the present invention is an amide resin having at least one structure represented by the following formula (1) or (2) and an alkali-soluble functional group:

When the resin composition of the present invention contains a resin having an imine bond directly bonded to a cyclohexane ring or a benzene ring, a cured product having excellent toughness and heat resistance can be obtained. In particular, the amidoimide resin having the structure represented by (1) has excellent light transmittance, and therefore can improve the resolution of the resin composition. In the resin composition of the present invention, the component (A) preferably has transparency. For example, in a dried coating film of the component (A) of 25 μm, the transmittance of light having a wavelength of 365 nm is preferably 70% or more.

The content of the structure of formula (1) and (2) in the component (A) of the resin composition of the present invention is preferably 10 to 70% by mass. By using this resin, a cured product having excellent solvent solubility, heat resistance, tensile strength, elongation, and other physical properties and dimensional stability can be obtained. It is preferably from 10 to 60% by mass, more preferably from 20 to 50% by mass.

The amide resin having the structure represented by formula (1), especially the resin having the structure represented by formula (3A) or (3B), has excellent physical properties such as tensile strength and elongation and dimensional stability. Better:

(In formulas (3A) and (3B), R is a monovalent organic group, and preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group, preferably a direct bond, CH ₂ or C(CH ₃ ) ₂ and other alkylene groups). In the resin composition of the present invention, based on the viewpoints of solubility and mechanical properties, a resin having a structure of 10 to 100% by mass of formulas (3A) and (3B) can be preferably used as the (A) component. More preferably, it is 20 to 80% by mass.

In the resin composition of the present invention, as the component (A), based on the viewpoints of solubility and mechanical properties, an amide containing 5-100 mol% of the structure of formula (3A) and (3B) can be preferably used Imine resin. It is more preferably 5 to 98 mol%, still more preferably 10 to 98 mol%, and most preferably 20 to 80 mol%.

And, as an amide resin having a structure represented by formula (2), especially a resin having a structure represented by formula (4A) or (4B),

(In formulas (4A) and (4B), R is a monovalent organic group, and preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group, preferably a direct bond, CH ₂ or C(CH ₃ ) ₂ and other alkylene groups) are preferable because a cured product with excellent mechanical properties such as tensile strength and elongation can be obtained. In the resin composition of the present invention, from the viewpoint of solubility and mechanical properties, as the component (A), a resin having a structure of 10 to 100% by mass of formulas (4A) and (4B) can be preferably used. More preferably, it is 20 to 80% by mass.

As the component (A) in the composition of the present invention, based on the reason that the structure of formula (4A) and (4B) containing 2~95 mol% of the amide resin can exhibit good mechanical properties, it can be compared Use it well. More preferably, it is 10 to 80 mole%.

The component (A) can be obtained by conventional methods. The amide resin having the structure of (1) can be obtained using, for example, a diisocyanate compound having a biphenyl skeleton and cyclohexane polycarboxylic acid anhydride.

Examples of diisocyanate compounds having a biphenyl skeleton are 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-diethyl -1,1'-biphenyl, 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl -1,1'-biphenyl, 4,4'-diisocyanate-3,3'-di-trifluoromethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2' -Di-trifluoromethyl-1,1'-biphenyl, etc. In addition, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate can also be used.

Cyclohexane polycarboxylic acid anhydride is exemplified by cyclohexane tricarboxylic acid anhydride, cyclohexane tetracarboxylic acid anhydride, and the like.

And, the amide resin with the structure of (2) can be used For example, the above-mentioned diisocyanate having a biphenyl skeleton and a polycarboxylic anhydride having two acid anhydride groups can be obtained.

Polycarboxylic anhydrides with 2 acid anhydride groups are listed as pyromellitic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3',4 ,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-2, 2',3,3'-tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-bis( 2,3-Dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane Dianhydride, 2,3-bis(3,4-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl) dianhydride, bis(3,4-dicarboxyphenyl) ether two Anhydride, ethylene glycol bistrimellitic acid anhydride ester and other alkanediol bishydroxy trimellitate, etc.

The (A) component of the resin composition of the present invention has an alkali-soluble functional group in addition to the structure of the above formulas (1) and (2). By having alkali-soluble functional groups, it becomes a resin composition that can be developed by alkali. The alkali-soluble functional group contains a carboxyl group, a phenolic hydroxyl group, a sulfo group, etc., preferably a carboxyl group.

The acid value of the component (A) of the resin composition of the present invention is preferably in the range of 20 to 120 mgKOH/g, more preferably in the range of 30 to 100 mgKOH/g. By making the acid value of the component (A) within the above-mentioned range, good alkali development can be achieved, and a pattern of a normal cured product can be formed. Although the weight average molecular weight of the component (A) of the resin composition of the present invention varies depending on the resin skeleton, it is generally preferably 2,000 to 150,000. When the weight average molecular weight is above 2,000, the dry coating film has no tackiness, and the moisture resistance and resolution of the coating film after exposure Good sex. On the other hand, when the weight average molecular weight is 150,000 or less, the developability and storage stability are good. It is more preferably 5,000 to 100,000.

In addition, specific examples of the component (A) include the UNDIC V-8000 series of DIC Co., Ltd. and the SOXR-U of Nippon Advanced Paper Co., Ltd.

The resin composition of the present invention may also contain a resin having an alkali-soluble functional group (hereinafter also referred to as (A1) component) different in structure from the (A) component. By containing the component (A1), a dry film with good adhesion between the resin layer and the substrate is obtained. Therefore, the dry film has excellent workability. The so-called disagreement between the structure and the component (A) refers to the structure without formulas (1) and (2). The alkali-soluble functional group of the component (A1) is the same as the alkali-soluble functional group of the component (A). (A1) The component is preferably a carboxyl group-containing resin using epoxy resin as a starting material, a carboxyl group-containing resin having a urethane skeleton (also called a carboxyl group-containing urethane resin), The copolymerization structure of saturated carboxylic acid contains carboxyl group-containing resins, phenolic compounds as starting materials, carboxyl group-containing resins, and their carboxyl group-containing resins have one carboxyl group and more than one (methyl) ) At least any one of carboxyl-containing resins made of acryl-based compounds. The specific example of (A1) component is illustrated below.

(1) Copolymerization of unsaturated carboxylic acid such as (meth)acrylic acid with unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Resins containing carboxyl groups.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., are glycolized with carboxyl-containing dimethylolpropionic acid, dimethylolbutyric acid, etc. Combine And polycarboxylate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and phenolic hydroxyl groups Carboxyl group-containing urethane resin obtained by the polyaddition reaction of glycol compounds such as alcoholic hydroxyl compounds.

(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc. are combined with polycarboxylate polyol, polyether polyol, and polyester polyol Amines obtained by the polyaddition reaction of alcohols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, etc. A urethane resin with a carboxyl group at the end formed by the reaction of the end of a carbamic acid ester resin with an acid anhydride.

(4) Diisocyanate, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisxylenol epoxy resin , Bisphenol-type epoxy resin and other bifunctional epoxy resin (meth)acrylate or its partial acid anhydride modified product, carboxyl-containing diol compound and diol compound polyaddition reaction of carboxyl-containing photosensitive Urethane resin.

(5) In the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added to make Terminal (meth)acrylated carboxyl group-containing photosensitive urethane resin.

(6) In the synthesis of the resin of (2) or (4) above, the molar reactants such as isophorone diisocyanate and pentaerythritol triacrylate are added to have one isocyanate group and more than one (methyl) ) Acrylic acid It is a photosensitive urethane resin containing a carboxyl group whose terminal is (meth)acrylated.

(7) Reacting a bifunctional or more multifunctional epoxy resin as described later with (meth)acrylic acid, and adding phthalic anhydride, tetrahydrophthalic anhydride, A carboxyl group-containing photosensitive resin made of dibasic acid anhydrides such as hexahydrophthalic anhydride. Here, the epoxy resin is preferably solid.

(8) Furthermore, the polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of the bifunctional epoxy resin described later with epichlorohydrin is reacted with (meth)acrylic acid, and the resulting hydroxyl group is added with a dibasic acid anhydride A photosensitive resin containing carboxyl groups. Here, the epoxy resin is preferably solid.

(9) Add cyclic ethers such as ethylene oxide or cyclic carbonates such as propylene carbonate to polyfunctional phenolic compounds such as novolac, and partially esterify the obtained hydroxyl groups with (meth)acrylic acid to make the remaining A photosensitive resin containing carboxyl group formed by the reaction of the hydroxyl group and polybasic acid anhydride.

(10) In the resins of (1) to (9), glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate and other molecules have an epoxy group and A carboxyl group-containing photosensitive resin composed of one or more (meth)acryloyl compounds.

(A1) The components are not limited to those using these, and one type may be used, or plural types may be mixed and used. In addition, the so-called (meth)acrylate is a general term for acrylate, methacrylate and their mixture, and the same applies to similar expressions below.

(A1) The acid value and weight average molecular weight of the component are the same as (A) It is divided into the same range of acid value and weight average molecular weight. The blending amount of the (A1) component is preferably from 5 mass% to 50 mass%, and more preferably from 10 mass% to 30 mass% with respect to 100 parts by mass of the total of (A) component and (A1) component. By being in the above range, a cured product having good toughness and heat resistance can be obtained.

〈(B) Ingredient〉

The resin composition of the present invention contains (B) inorganic particles having an average particle diameter of 200 nm or less. (B) The average particle diameter of the inorganic particles is preferably at most 150 nm, more preferably at most 100 nm. The reason why the average particle diameter of the inorganic particles is 200 nm or less is as follows. That is, generally, the exposure of the resin composition uses an ultraviolet wavelength with a wavelength of 450 nm or less. In order to achieve good resolution of the resin composition, it is necessary to suppress the scattering of light. However, when the inorganic particles in the resin composition are irradiated with light, the light will cause scattering. The smaller the particle size, the less the dispersion, but as a result of the review conducted by the inventors, it was found that by setting the particle size of the inorganic particles to 200 nm or less which is about half of the ultraviolet wavelength for exposure, the resolution can be greatly improved. The average particle size here is the value measured by the laser diffraction method. Examples of measuring devices using the laser diffraction method include Nanotrac Wave.

When measuring the average particle size of the inorganic particles in the cured product, the surface of the cured product is treated with plasma and etched to become a state where the inorganic particles are visible, and the inorganic particles are observed by SEM (Scanning Electron Microscope). When obtaining the average particle diameter of the inorganic particles, the diameter of the observed inorganic particles is measured in the range of 1 μm ² , and the operation is performed 5 times including other parts, and the average value of the diameter of the inorganic particles is calculated. The plasma treatment system uses, for example, MARCH PLASMA SYSTEM INC AP-1000 as the device, and is set to power: 500W, pressure: 300 Torr, gas: Ar, and treatment time: 10 minutes.

Inorganic particles can be used, for example, silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, boehmite (Boehmite), mica powder, hydrotalcite, Silitin (silica material), Silikolloid ( Silica gel) and other conventionally used inorganic fillers. Among them, silica with a small linear expansion coefficient is preferably used. Moreover, these inorganic particles may be used individually by 1 type, and may be used in combination of 2 or more types.

The blending amount of the (B) component in the resin composition of the present invention is relative to 100 parts by mass of the total of the (A) component and the (A1) component (when the (A1) component is not included, it is 100 parts by mass of the (A) component) It is preferably from 10 to 150 parts by mass, more preferably from 30 to 120 parts by mass. By setting the component (B) to 10 parts by mass or more, the effect of reducing the coefficient of linear expansion can be sufficiently obtained. On the other hand, by setting the component (B) to 150 parts by mass or less, the resin of the present invention can be prevented from being applied The workability of the composition deteriorates.

In the resin composition of the present invention, as described above, silica having a small linear expansion coefficient can be preferably used as the component (B). In this case, the silica is preferably one whose surface has been treated with a silane coupling agent. The reason is that it can prevent precipitation or aggregation after being dispersed in a liquid, and as a result, it has excellent storage stability. In addition, the resin composition can be stably thrown in without agglomeration at the time of compounding. Furthermore, the wettability of the resin and particles of the obtained cured product can be improved.

The organic groups contained in the silane coupling agent are, for example, vinyl, epoxy, styryl, methacryloxy, acryloxy, Amine group, urea group, chloropropyl group, mercapto group, polysulfide group, isocyanate group, etc. The silane coupling agent may be used singly or in combination of two or more.

〈(C) Ingredient〉

The resin composition of the present invention contains (C) a photopolymerization initiator. (C) The photopolymerization initiator preferably contains an oxime ester system containing a structure represented by the general formula (I), an α-aminoacetophenone system containing a structure represented by the general formula (II), and One or two or more selected from the group consisting of the structure represented by the general formula (III) and the titanocene system represented by the general formula (IV).

In the general formula (I), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzyl group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzyl group.

The phenyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and the alkyl chain may contain one or more oxygen atoms. Moreover, it may be substituted by more than one hydroxyl group. The cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 5 to 8 carbon atoms. The alkanoyl group represented by R ¹ and R ² is preferably an alkanoyl group having 2 to 20 carbon atoms. The benzyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like.

In the general formula (II), R ³ and R ⁴ each independently represent an alkyl group or arylalkyl group with 1 to 12 carbons, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbons, Or two may be bonded to form a cyclic alkyl ether group.

In the general formula (III), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, cyclohexyl group, cyclopentyl group, aryl group, or aryl group substituted with halogen atom, alkyl group or alkoxy group , Or a carbonyl group with 1 to 20 carbons (except when both are carbonyls with 1 to 20 carbons).

In the general formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group, and a heterocyclic-containing halogenated aryl group.

Specific examples of the oxime ester-based photopolymerization initiator are 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzyloxime)], ethyl ketone, 1- [9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and the like. Commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02, N-1919, NCI-831 manufactured by Adeka, etc. manufactured by BASF in Japan. A photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiator having a carbazole structure can also be preferably used. Specific examples are oxime ester compounds represented by the following general formula (V).

(In the general formula (V), X represents a hydrogen atom, an alkyl group with 1 to 17 carbons, an alkoxy group with 1 to 8 carbons, a phenyl group, and a phenyl group (the alkyl group with 1 to 17 carbons, the carbon number Alkoxy, amino, alkylamino or dialkylamino substituted with 1~8 alkyl group), naphthyl (substituted with 1~17 alkyl group, carbon number 1 ~8 alkoxy group, amino group, alkylamino group or dialkylamino group having an alkyl group with 1 to 8 carbons), Y and Z respectively represent a hydrogen atom, an alkyl group with 1 to 17 carbons, Alkoxy, halo, phenyl, phenyl with 1~8 carbons (alkyl with 1~17 carbons, alkoxy with 1~8 carbons, amino groups, alkyls with 1~8 carbons) Alkylamino group or dialkylamino group substituted), naphthyl (alkyl group with carbon number 1~17, alkoxy group with carbon number 1~8, amino group, alkyl group with carbon number 1~8 Alkylamino group or dialkylamino group substitution), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents a bond, or alkylene, vinylene, and ethylene with 1 to 10 carbon atoms Phenyl, biphenylene, pyridinyl, naphthylene, thienyl, anthracenyl, thienyl, furanyl, 2,5-pyrrol-diyl, 4,4'-stilbene (stilbene ) Diyl, 4,2'-styrenediyl, n is an integer of 0 or 1).

Especially, in the general formula (V), X and Y are each methyl or ethyl, Z is methyl or phenyl, n is 0, Ar is preferably a bond, or phenylene, naphthylene, thienyl or Thienylene (thienylene).

In addition, preferred carbazole oxime ester compounds can also be exemplified by compounds represented by the following general formula (VI).

(In the general formula (VI), R ¹ represents an alkyl group with 1 to 4 carbon atoms, or a phenyl group that can be substituted with a nitro group, a halogen atom or an alkyl group with 1 to 4 carbon atoms, and R ² represents the number of carbon atoms Alkyl group with 1 to 4, alkoxy group with 1 to 4 carbon atoms, or phenyl group which can be substituted by alkyl group with 1 to 4 carbon atoms or alkoxy group. R ³ means that it can be connected by oxygen atom or sulfur atom , Alkyl group with 1 to 20 carbon atoms which can be substituted by phenyl group, benzyl group which can be substituted by alkoxy group with 1 to 4 carbon atoms, R ⁴ represents a nitro group, or XC(=O)- As for the acyl group, X represents an aryl group, a thienyl group, a morpholinyl group, a thiophenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, or a structure represented by the following formula (VII)).

As a specific example of the α-aminoacetophenone-based photopolymerization initiator, (4-morpholinylbenzyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, Japan Made by BASF Corporation), 4-(Methylthiobenzyl) Yl)-1-methyl-1-morpholineethane (Irgacure 907, trade name, manufactured by BASF Japan), 2-(dimethylamino)-2-[(4-methylphenyl)methyl] Commercially available compounds such as -1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379, trade name, manufactured by BASF Corporation, Japan) or their solutions.

Specific examples of phosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzyl diphenyl phosphine oxide, bis(2,4,6-trimethylbenzyl) -Phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Commercial products include Lucirin TPO and Irgacure 819 manufactured by BASF.

The titanocene-based photopolymerization initiator is enumerated as bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) -Phenyl) titanium. Commercial products are listed as Irgacure 784 manufactured by BASF Corporation of Japan, etc.

Other photopolymerization initiators include, for example, benzyl, benzyl methyl ether, benzyl ethyl ether, benzyl isopropyl ether, and benzyl alkyl ethers; acetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and other acetophenones; 2-methyl Anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; acetophenone dimethyl acetal, benzyl dimethyl acetal, etc. Aldehydes; benzophenones such as benzophenone; xanthones; various peroxides such as 3,3',4,4'-tetra-(tert-butylperoxycarbonyl)benzophenone Class; 1,7-bis(9-acridinyl)heptane and so on.

In the resin composition of the present invention, in addition to the above-mentioned photopolymerization initiator, it may also be combined with ethyl N,N-dimethylaminobenzoate, N,N-di Isoamyl methylamino benzoate, pentyl 4-dimethylamino benzoate, triethylamine, triethanolamine and other conventionally used photosensitizers are used in combination of one or more . Furthermore, when a deeper light curing depth is required, a 3-substituted coumarin dye, leuco dye, etc. may be combined as a curing aid as needed.

In the resin composition of the present invention, the blending ratio of the (C) component is per 100 parts by mass of the total of the (A) component and the (A1) component (when the (A1) component is not included, it is 100 parts by mass of the (A) component) , Preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 15 parts by mass. By setting the blending amount of the component (C) in the above range, radicals necessary for the reaction can be sufficiently generated, and since light can be transmitted to the deep part, problems such as brittleness of the hardened product can be avoided. Moreover, (C)component may be used individually by 1 type, and may be used in combination of 2 or more types.

〈(D)Component〉

The resin composition of the present invention contains (D) a compound having an unsaturated double bond. The component (D) can be photocured by irradiation of active energy rays, so that the resin composition of the present invention is insolubilized in an aqueous alkali solution, or contributes to insolubilization. The compound can be used conventionally known polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, epoxy (meth)acrylate, (Base) acrylate, urethane (meth)acrylate, specific examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethyl Diacrylates of glycol, polyethylene glycol, propylene glycol and other glycols; N,N-dimethyl propylene Acrylic amines such as amide, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide; N,N-dimethylaminoethyl acrylate, N,N- acrylate Amino alkyl acrylates such as dimethylaminopropyl ester; polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, ginseng-hydroxyethyl isocyanurate, etc. or such ethylene oxide Alkyl adducts, propylene oxide adducts, or ε-caprolactone adducts and other polyvalent acrylates; phenoxy acrylate, bisphenol A diacrylate, and epoxy of these phenols Polyvalent acrylic esters such as ethane adducts or propylene oxide adducts; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl iso Polyvalent acrylates of glycidyl ethers such as cyanurate; not limited to the above, but can be exemplified by direct acrylic acid of polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol, etc. Esterification, or at least any one of acrylates and melamine acrylates formed by urethane acrylate through diisocyanate, and methacrylates corresponding to the aforementioned acrylates.

Furthermore, epoxy acrylate resin obtained by reacting polyfunctional epoxy resin such as cresol novolak type epoxy resin with acrylic acid, or the hydroxyl group of epoxy acrylate resin and the hydroxyl group of pentaerythritol triacrylate etc. Epoxy urethane acrylate compound formed by the reaction of half urethane of diisocyanate such as acrylate and isophorone diisocyanate. These epoxy acrylate resins do not reduce the dryness to the touch, but can improve the photocurability. The compound having an ethylenically unsaturated group in the molecule described above may be used alone or in combination of two or more kinds.

(D) The blending ratio of the components is between (A) and (A1) Per 100 parts by mass in total (when component (A1) is not included, it is 100 parts by mass of (A) component), preferably 1-60 parts by mass, more preferably 5-50 parts by mass, still more preferably 10-40 parts by mass Copies. By setting the blending amount of the component (D) in the above-mentioned range, good photoreactivity can be obtained, and at the same time, it has heat resistance.

〈(E) Thermosetting resin〉

In order to further improve heat resistance, the resin composition of the present invention preferably contains (E) thermosetting resin (hereinafter also referred to as "(E) component"). Examples of thermosetting resins include, for example, polyfunctional epoxy compounds, polyfunctional oxetane compounds, epithiopropane resins, etc., having two or more cyclic ether groups and/or cyclic thioether groups, and polyisocyanate compounds in the molecule. , Protected isocyanate compounds and other compounds having more than two isocyanate groups in one molecule, or compounds with protected isocyanate groups, amine compounds and derivatives such as melamine resins, benzoguanidine resins, bismaleimide, oxazines, Conventional thermosetting resins such as cyclic carbonate compounds and carbodiimide resins.

As the epoxy resin, a conventional multifunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin can be liquid, solid or even semi-solid. Examples of multifunctional epoxy resins are bisphenol A type epoxy resin; brominated epoxy resin; novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidyl amine type Epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; dixylenol type or diphenol type epoxy resin or a mixture of these ; Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin; Tetrahydroxyphenyl ethane type epoxy resin; Heterocyclic ring Oxygen resin; diglycidyl phthalate resin; tetraglycidyl xylylene dimethanyl ethane resin; epoxy resin containing naphthyl group; epoxy resin with dicyclopentadiene skeleton; methyl Glycidyl acrylate copolymerized epoxy resin; cyclohexyl maleimide and glycidyl methacrylate copolymerized epoxy resin; epoxy modified polybutadiene rubber derivative; CTBN modified ring Oxygen resin, but not limited to these. The epoxy resin is preferably bisphenol A type or bisphenol F type novolac type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolac type (biphenyl aralkyl Type) epoxy resin, naphthalene type epoxy resin or a mixture of these.

In particular, the thermosetting resin is preferably an epoxy resin having a naphthalene skeleton. Because naphthalene has a flat structure, it can reduce the coefficient of linear expansion and further improve the heat resistance. Moreover, these thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more types. Commercial products of epoxy resins with a naphthalene skeleton include, for example, ESN-190 and ESN-360 manufactured by Nippon Steel Chemicals, EPICRON HP-4032 and EPICRON HP-4032D manufactured by DIC.

From the viewpoint of resolution, the (E) component is preferably one without discoloration. The component (E) is preferably a thermosetting resin having an alicyclic skeleton, for example, preferably a thermosetting resin containing a dicyclopentadiene skeleton, most preferably an epoxy containing a dicyclopentadiene skeleton Resin. In addition, a thermosetting resin having an alicyclic skeleton is preferable because it can obtain a glass transition temperature improvement effect more than an epoxy resin having a chain skeleton.

The blending ratio of (E) component is 100 parts by mass of the total of (A) component and (A1) component (when (A1) component is not included, it is 100 mass of (A) component) Parts), preferably from 10 to 100 parts by mass, more preferably from 10 to 80 parts by mass. By setting the blending amount of the (E) component within the above range, a composition having heat resistance and good developability and photoreactivity can be obtained.

When (E) thermosetting resin is contained in the resin composition of the present invention, a thermosetting catalyst may be contained. Examples of thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl- 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4-(dimethyl Amine)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine and other amine compounds , Dihydrazine adipate, dihydrazine sebacate and other hydrazine compounds; phosphorus compounds such as triphenylphosphine. In addition to these, guanidine, acetoguanidine, benzoguanidine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, and 2-vinyl can also be used. -2,4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine‧Isocyanuric acid adduct, 2,4-diamino-6-methyl S-triazine derivatives such as allyl oxyethyl-S-triazine and isocyanuric acid adducts.

Commercially available thermosetting catalysts include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all the trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT manufactured by SAN-APRO. 3503N, U-CAT 3502T (all are the trade names of protected isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts), etc. These may be used individually by 1 type, and may combine 2 or more types. In the resin composition of the present invention, the blending amount of the thermosetting catalyst is 100 relative to the total of (A) component and (A1) component Parts by mass (when the component (A1) is not included, 100 parts by mass of the (A) component), it is preferably from 0.1 to 10 parts by mass, more preferably from 0.1 to 5.0 parts by mass.

Furthermore, in the resin composition of the present invention, in order to prepare the composition or to adjust the viscosity for coating on a substrate or a carrier film, an organic solvent can be used. Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, Carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, acetic acid Butyl ester, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; Aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

<other>

The resin composition of the present invention is characterized by comprising (A) an amide resin having a structure represented by at least one of the above formula (1) or (2) and an alkali-soluble functional group, and (B) an average particle size of Inorganic particles below 200nm, (C) photoreaction initiator, and (D) compounds having unsaturated double bonds, there are no special restrictions other than that. For example, the resin composition of the present invention may optionally be added with conventional and conventional coloring agents (for example, white coloring agents such as titanium oxide, carbon Black colorants such as black, titanium black, phthalocyanine blue, phthalocyanine green, disazo yellow, etc.), thermal polymerization inhibitors, thickeners, defoamers, leveling agents, etc.

The resin composition of the present invention is preferably used for the formation of an insulating cured film of a printed wiring board, more preferably for the formation of an insulating permanent film, and is preferably used for the formation of a protective layer, a solder resist, and an interlayer insulating material. In addition, the resin composition of the present invention can also be used for the formation of flux barriers. The resin composition of the present invention may be a liquid type, or a dry film type obtained by drying a liquid resin composition. The liquid resin composition may be a two-component type or the like from the viewpoint of storage stability, or a one-component type.

[Dry film]

The dry film of the present invention has a resin layer obtained by coating the resin composition of the present invention on a film (hereinafter also referred to as "carrier film") and then drying. The dry film of the present invention uses organic solvents to dilute and adjust the resin composition of the present invention to a proper viscosity, using a chipped wheel coater, blade coater, die lip coater, rod coater, and extrusion Coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., coat the carrier film to a uniform thickness, and usually dry at a temperature of 50-130 ℃ for 1-30 In minutes. The coating film thickness is not particularly limited, but it is generally set appropriately in the range of 5 to 150 μm, preferably 10 to 60 μm in terms of the film thickness after drying. The film is not limited to a carrier film, and may be a protective film.

As the carrier film, a plastic film can be suitably used, preferably a polyester film such as polyethylene terephthalate, a polyimide film, and a polyimide imide Film, polypropylene film, polystyrene film and other plastic films. The thickness of the carrier film is not particularly limited, and is generally selected appropriately within the range of 10 to 150 μm.

After the resin composition of the present invention is coated on the carrier film, for the purpose of preventing dust from adhering to the surface of the coating film, a protective film that can be peeled off on the surface of the film can also be used. The peelable protective film can use, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc., as long as the adhesive force between the film and the protective film is lower than the adhesive force between the film and the carrier film when the protective film is peeled off Who can.

After coating the resin composition of the present invention on the carrier film, the volatilization drying can be carried out by using a hot-air circulation drying oven, IR oven, hot plate, convection oven, etc. (using a heat source equipped with an air heating method using steam to dry The method of convective contact of hot air in the machine and the method of blowing from the nozzle to the support) are carried out.

[Hardened material]

The cured product of the present invention is obtained by curing the resin composition of the present invention and the resin layer of the dry film of the present invention. The cured product of the present invention can be exposed by applying the resin composition of the present invention and evaporating and drying the solvent, or irradiating the dry film with active energy rays, so that the Part of the exposed part is cured.

[Printed Wiring Board]

The printed wiring board of the present invention is provided with the cured product of the present invention. The printed wiring board of the present invention can be directly applied to the curable resin composition of the present invention The method of coating on the printed wiring board is obtained by the method of using the dry film of the present invention.

When manufacturing the printed wiring board of the present invention by the direct coating method, the resin composition of the present invention can be directly coated on the printed circuit board forming the circuit, and after the coating film of the resin composition is formed, the pattern is directly Exposure by irradiating active energy rays such as laser light, or selectively irradiating active energy rays through a patterned photomask, and developing the unexposed area with a dilute alkali aqueous solution to form a resist pattern. Furthermore, the resist pattern is irradiated with active energy rays of, for example, 500-2000 mJ/cm ² , and heated to a temperature of, for example, about 140 to 180° C. to harden, thereby manufacturing a printed wiring board with a hardened pattern. In addition, the irradiation of the resist pattern by the active energy rays is performed to substantially complete the curing reaction of the unreacted component (D) under the exposure when the resist pattern image is formed.

When a dry film is used, the dry film of the present invention is laminated on a printed wiring board forming a circuit, and the resin layer is laminated, and after exposure as described above, the carrier film is peeled off and developed. Subsequently, the resin layer is irradiated with active energy rays and heated to a temperature of, for example, about 140 to 180° C. to be cured, thereby manufacturing a printed wiring board with a pattern of the cured product. In addition, the pattern of the hardened film can be formed by photolithography, or by screen printing or the like.

The exposure machine used for the irradiation of active energy rays only needs to be equipped with a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, mercury short-arc lamp, etc., and a device that can irradiate ultraviolet rays in the range of 350 to 450 nm. Furthermore, it can also be used. The direct rendering device is a direct rendering device that draws an image by direct active energy lines from CAD data from a computer. As long as the light source of the direct drawing device uses mercury short-arc lamps, LEDs, and lasers with a maximum wavelength of 350~410nm, either gas laser or solid laser can be used. The exposure dose for resist pattern image formation varies with the film thickness, etc., but it is generally 20~1500mJ/cm ² , preferably in the range of 20~1200mJ/cm ² .

The imaging method can be dipping, leaching, spraying, brushing, etc., and can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. The alkaline aqueous solution is used as the developing solution.

Example

Hereinafter, the resin composition of the present invention will be described in detail using examples.

<Examples 1 to 25 and Comparative Examples 1 to 3>

According to the following formulas in Tables 1 to 4, the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared. The obtained resin composition was coated on the entire surface of a copper foil substrate for evaluation with a pattern formed by screen printing, dried at 80°C for 30 minutes, and allowed to cool to room temperature. Subsequently, on the obtained evaluation substrate, using an exposure device equipped with a high-pressure mercury lamp, the resist pattern was exposed with an optimal exposure amount, and the image was developed with a 1% by mass sodium carbonate aqueous solution at 30°C for 90 seconds under a pressing pressure of 0.2 MPa. After forming the resist pattern of the cured product, irradiate it with ultraviolet rays under the condition of a cumulative exposure of 1000mJ/cm ² in a UV conveyor furnace, and then heat it at 180°C for 60 minutes to cure it. In addition, the amide resin (A-1), other resins (A1-1), and (A1-2) were synthesized using the following synthesis method. The obtained evaluation substrate was evaluated for resolution, tensile strength, elongation, coefficient of linear expansion, and glass transition point. The average particle size of the inorganic particles in Tables 1 to 4 is the measured value obtained by the laser diffraction method. In addition, the optimal exposure amount is obtained by the following procedure.

〈Optimal exposure〉

According to the formulas in the following Tables 1 to 4, the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared. Next, the copper-clad laminate substrate was polished by buff rolls, washed with water, dried, and the obtained resin composition was coated by a screen printing method, and dried in a hot air circulation drying oven at 80° C. for 30 minutes. After drying, it was exposed through a photomask (Eastman Kodak Co., Step Tablet No. 2) using a high-pressure mercury lamp exposure device. The irradiated test piece was used as a test piece, and the developing solution (1% by mass sodium carbonate aqueous solution at 30°C) was developed for 60 seconds with a spray pressure of 2 kg/cm ² , and then the number of remaining coating films was visually judged. Set the exposure level of the residual coating film to 10 segments as the appropriate exposure level.

<Synthesis of amide resin (A-1) (synthesis example 1)>

Into a flask equipped with a stirring device, a thermometer and a condenser were fed GBL (γ-butyrolactone) 848.8g, MDI (diphenylmethane diisocyanate) 57.5g (0.23 mol), DMBPDI (4,4'- Diisocyanate-3,3'-dimethyl-1,1'-biphenyl) 59.4g (0.225 mol) and TMA (trimellitic anhydride) 67.2g (0.35 mol) and TMA-H (cyclohexane-1, 3,4-tricarboxylic acid-3,4-acid anhydride) 29.7g (0.15 mol), while stirring, be careful to raise the temperature to 80°C under heat, dissolve and react at this temperature within 1 hour, and then raise the temperature to 160°C within 2 hours, and react at this temperature for 5 hours . The reaction proceeds with the foaming of carbon dioxide gas, and the system becomes a brown transparent liquid. A solution of polyamidoimide resin (A1) with a viscosity of 7Pa‧s at 25℃ and a resin solid content of 17% and a solution acid value of 5.3 (KOHmg/g) (the resin is dissolved in γ-butyrolactone) The resin composition). In addition, the solid acid value of the resin was 31.2 (KOHmg/g). Also, as a result of gel permeation chromatography (GPC) measurement, the weight average molecular weight was 34,000. The polyamide imide resin (A-1) is a resin having the structure of the above formulas (1) and (2) and a carboxyl group.

<Synthesis of other resins (A1-1) (Synthesis example 2)>

Feed o-cresol novolac epoxy resin into 600 g of diethylene glycol monoethyl ether acetate [EPICLON N-695 manufactured by DIC, softening point 95℃, epoxy equivalent 214, average number of functional groups 7.6] 1070 g (glycidyl number (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone, heated and stirred to 100°C, and uniformly dissolved. Next, 4.3 g of triphenylphosphine was fed, and after heating to 110° C. for reaction for 2 hours, the temperature was raised to 120° C. for further reaction for 12 hours. 415 g of aromatic hydrocarbons (Solvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic anhydride were fed into the resulting reaction liquid, and reacted at 110°C for 4 hours. After cooling, A cresol novolak type carboxyl group-containing resin solution with a solid content of 89 mgKOH/g and a solid content of 65% was obtained. The obtained resin is called other resin (A1-1).

<Synthesis of other resins (A1-2) (Synthesis example 3)>

Feed the novolak-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name "Shonol CRG951", OH equivalent: 119.4) 119.4 into an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device g. Potassium hydroxide 1.19g and toluene 119.4g, while stirring, replace the system with nitrogen, and heat up. Then, 63.8 g of propylene oxide was slowly added dropwise, and the reaction was carried out at 125 to 132° C. and 0 to 4.8 kg/cm ² for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added and mixed in the reaction solution to neutralize potassium hydroxide to obtain propylene oxide of a novolac type cresol resin with a non-volatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Reaction solution. The phenolic hydroxyl group adds an average of 1.08 mol of alkylene oxide per equivalent.

Next, 293.0g of the alkylene oxide reaction solution of the novolak type cresol resin, 43.2g of acrylic acid, 11.53g of methanesulfonic acid, 0.18g of methylhydroquinone and 252.9g of toluene were fed into a mixer equipped with a mixer, a thermometer and an air blowing pipe In the reactor, air was blown at a rate of 10 ml/min, and the reaction was carried out at 110°C for 12 hours while stirring. The water produced by the reaction was used as an azeotropic mixture with toluene and 12.6 g of water was distilled out. After cooling to room temperature, the resulting reaction solution was neutralized with 35.35 g of a 15% sodium hydroxide aqueous solution, followed by washing with water. Subsequently, using an evaporator, while replacing toluene with 118.1 g of diethylene glycol monoethyl ether acetate, the toluene was distilled off to obtain a novolac type acrylate resin solution. Next, 332.5g of the obtained novolac type acrylate resin solution and 1.22g of triphenylphosphine were fed into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10ml/min, and added slowly while stirring 60.8 g of tetrahydrophthalic anhydride, reacted at 95~101°C for 6 hours. obtain A resin solution of a carboxyl-containing photosensitive resin with a solid acid value of 88mgKOH/g and a non-volatile content of 71%. Hereinafter, the obtained resin is referred to as another resin (A1-2).

<Resolution>

The observation of the pattern of the cured film of the produced evaluation substrate was carried out with a scanning electron microscope (SEM) of 1,000 times, and the evaluation was performed according to the following evaluation criteria. The results obtained are recorded in Tables 1 to 4.

AA: It is possible to form lines and spaces of 10 μm or less.

A: It is possible to form lines and spaces of 15 μm or less.

B: It is possible to form lines and spaces of 25 μm or less.

C: Lines and spaces of 25 μm cannot be formed.

〈Tensile strength‧Elongation (Toughness)〉

For the cured film (10mm×40mm) obtained by curing the resin compositions of Examples 1-25 and Comparative Examples 1-3 under the same conditions as above, Autograph AG-X manufactured by Shimadzu Corporation, at a speed of 1mm/min Perform a tensile test. The results obtained are recorded in Tables 1 to 4. When the breaking point stress and elongation are large, the strength and toughness are excellent.

A: Breaking point stress 80N/mm ² or more / elongation 3% or more

B: Breaking point stress 50N/mm ² or more and less than 80N/mm ² / Elongation 2% or more and less than 3%

C: The stress at the breaking point is less than 50N/mm ² / the elongation is less than 2%

〈Coefficient of linear expansion‧Glass transition point (heat resistance)〉

Using TMA6100 manufactured by Seiko Instruments, the resin composition of Examples 1-25 and Comparative Examples 1 to 3 was cured under the same conditions as the above-mentioned 3mm×10mm hardened film while applying a load of 10g, while applying a constant load The temperature rise rate is 0℃~260℃ for tensile test. The coefficient of linear expansion (CTE) is calculated from the elongation of the cured film with respect to the temperature. In addition, the glass transition point (Tg) is obtained from the bending point. The results obtained are recorded in Tables 1 to 4. When Tg is higher and CTE is lower, heat resistance is excellent.

A: Tg above 180℃/CTE less than 40ppm

B: Tg 150℃ above 180℃/CTE below 50ppm and above 40ppm

C: Tg less than 150℃/CTE 50ppm or more

〈Dry film workability〉

Using a cloth gluer with a gap of 60 μm, the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were coated on a 38 μm thick polyethylene terephthalate (PET) film, and dried at 80°C for 30 minutes. Let it cool to room temperature to make a dry film with a resin layer. Cut the resin layer on the obtained PET film into a size of 10 cm square, and bend it diagonally. Check whether the resin layer is stably present on the PET in the form of a film during bending.

A: It is bent like PET and does not peel off from PET.

B: Although it did not peel off from PET, the bent part was broken.

C: The bent part was broken and peeled off from the PET.

<Visualization>

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were coated on a copper foil substrate, and after drying, a dry coating film was formed so that the coating film area became 10 cm×10 cm and the thickness became 50 μm. Pour 3L of 1% by mass sodium hydroxide aqueous solution into a beaker, and heat to 30°C to prepare a developing solution. In addition, the weight of the substrate on which the dried coating film was formed was measured. Next, the substrate was immersed in the developing solution and shaken for 1 minute to take out. After that, the substrate was immediately washed with water and dried, and then the weight was measured again. The developability was calculated from the weight change of the substrate, that is, (weight change of the substrate: g)/(volume of the developer: L) and evaluated. It can be seen that the higher the value of developability, the faster the developing speed. In addition, when a composition containing a general polyimide resin (manufactured by Air Water Co., Ltd., TECHMIGHT E2020), the developability is 0.01 g/L or less and is almost insoluble.

Amide resin (A-1): the resin synthesized in Synthesis Example 1 (resin solid content 17%)

Amide imine resin (A-2): SOXR-U (resin solid content 20%) (manufactured by Nippon High Paper Industry Co., Ltd.), which is equivalent to the formula (2) above Structured carboxyl-containing amide resin

Other resin (A1-1): The carboxyl-containing resin synthesized in Synthesis Example 2 (solid content 65%)

Other resins (A1-2): The carboxyl-containing resin synthesized in Synthesis Example 3 (solid content 71%)

Inorganic particles 1: Silica with an average particle size of 100nm

Inorganic particles 2: Silica with an average particle size of 50nm

Inorganic particles 3: Barium sulfate with an average particle size of 100nm

Inorganic particles 4: Silica with an average particle size of 1μm

Photopolymerization initiator 1: TPO manufactured by BASF

Photopolymerization initiator 2: IRG-369 manufactured by BASF

Photopolymerization initiator 3: IRG-OXE02 manufactured by BASF

Compound with unsaturated double bond 1: Dipentaerythritol hexaacrylate

Compound with unsaturated double bond 2: Dicyclopentadiene diacrylate

Thermosetting resin 1: Epoxy resin HP4032 (150eq) containing naphthalene skeleton (manufactured by DIC)

Thermosetting resin 2: Naphthol modified epoxy resin NC7000 (230eq) (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting resin 3: Biphenyl aralkyl epoxy resin NC3000 (275eq) (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting resin 4: epoxy resin XD-1000 (250eq) containing dicyclopentadiene skeleton (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting resin 5: Dicyclopentadiene skeleton epoxy resin HP-7200H (280eq) (manufactured by DIC Corporation)

Thermal hardening catalyst 1: Melamine

Thermal hardening catalyst 2: Dicyandiamide

It can be seen from Tables 1 to 4 that the resin composition of the present invention can obtain a cured product excellent in resolution, heat resistance, and toughness. Furthermore, it can be seen that the dry film obtained from the resin composition of the present invention has excellent workability.

Claims (9)

A curable resin composition characterized by comprising (A), (B), (C), (D) and (A1): (A) has at least one of the following formulas (1) and (2) Structure and alkali-soluble functional group of amide resin,

(B) Inorganic particles with an average particle size of 200nm or less, (C) photopolymerization initiator, (D) compound with unsaturated double bond, (A1) structure is different from the aforementioned (A) amide resin A resin having an alkali-soluble functional group; the compounding amount of the aforementioned (A1) component is 5 mass% or more and 30 mass% or less with respect to 100 parts by mass of the total of the aforementioned (A) component and the aforementioned (A1) component. Such as the curable resin composition of the first item in the scope of the patent application, wherein the aforementioned (B) inorganic particle type silica having an average particle diameter of 200 nm or less. For example, the curable resin composition of item 1 of the scope of patent application, which contains (E) thermosetting resin. For example, the curable resin composition of item 3 in the scope of patent application, wherein the aforementioned (E) thermosetting resin is an epoxy resin having an alicyclic skeleton. A dry film characterized by having a resin layer obtained by applying a curable resin composition as in any one of items 1 to 4 in the scope of the patent application to the film and drying it. A hardened product characterized by hardening a curable resin composition as in any one of items 1 to 4 in the scope of the patent application. A hardened product characterized by hardening the resin layer of the dry film as claimed in item 5 of the patent application. A printed wiring board characterized by being constructed with a cured product as described in item 6 of the scope of patent application. A printed wiring board characterized by being constructed with a hardened material as in item 7 of the scope of patent application.